European Journal of Organic Chemistry

Cover image for Vol. 2014 Issue 34

Early View (Online Version of Record published before inclusion in an issue)

Editor: Haymo Ross, Deputy Editor: Susan Wilkinson

Impact Factor: 3.154

ISI Journal Citation Reports © Ranking: 2013: 14/58 (Chemistry Organic)

Online ISSN: 1099-0690

Associated Title(s): Advanced Synthesis & Catalysis, Asian Journal of Organic Chemistry

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  1. Microreviews

    1. Frondosin Natural Products

      The Frondosins: An Unusual Synthetic and Stereochemical Journey

      Michael D. VanHeyst and Dennis L. Wright

      Article first published online: 28 NOV 2014 | DOI: 10.1002/ejoc.201403116

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      The first two syntheses of (+)-frondosin B, by Danishefsky and by Trauner, gave conflicting assignments for the single stereocenter at C8. Ensuing syntheses of frondosins B and A resolved this conflict and established that (+)-frondosin B is the R enantiomer. Wright's group showed that a late-stage stereochemical inversion occurred in a common intermediate of both their and Trauner's syntheses.

  2. Full Papers

    1. Amide Formation

      Iron/Caffeine as a Catalytic System for Microwave-Promoted Benzamide Formation

      Xavier Bantreil, Pauline Navals, Jean Martinez and Frédéric Lamaty

      Article first published online: 28 NOV 2014 | DOI: 10.1002/ejoc.201403173

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      Upon microwave activation, benzamides were formed directly from alcohols and amines in yields up to 84 % and TOFs (turnover frequencies) up to 33.6 h–1. Among the examined transition metals, only nontoxic and inexpensive FeCl2·4H2O along with caffeine as a stabilizing ligand provided the uniquely efficient catalytic system for the benzamide formation.

    2. C–H Functionalization

      Ceric Ammonium Nitrate (CAN) Promoted PdII-Catalyzed Substrate-Directed o-Benzoxylation and Decarboxylative o-Aroylation

      Sourav Kumar Santra, Arghya Banerjee, Nilufa Khatun and Bhisma K. Patel

      Article first published online: 27 NOV 2014 | DOI: 10.1002/ejoc.201403367

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      CAN can activate: Inexpensive ceric ammonium nitrate (CAN) is an efficient oxidant for the Pd-catalyzed substrate-directed o-benzoxylation and decarboxylative o-aroylation processes. In the presence of CAN, the reaction of directing arenes with carboxylic acids resulted in o-benzoxylated products, and that with α-keto acids led to the formation of o-aroylation products.

    3. IrIII-Catalyzed Direct C-7 Amidation of Indolines with Sulfonyl, Acyl, and Aryl Azides at Room Temperature

      Wei Hou, Yaxi Yang, Wen Ai, Yunxiang Wu, Xuan Wang, Bing Zhou and Yuanchao Li

      Article first published online: 27 NOV 2014 | DOI: 10.1002/ejoc.201403355

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      An IrIII-catalyzed C-7 selective C–H amidation of indolines with organic azides has been achieved. This method offers an environmentally benign, readily scalable synthesis for 7-aminoindolines. More importantly, acyl, sulfonyl, and aryl azides can be employed in this C–H amidation reaction under very mild reaction conditions (DCE = 1,2-dichloroethane).

    4. Asymmetric Synthesis

      Synthesis of (+)-6,7-Dimethoxy-1,2,3,4-tetrahydroisoquinoline-1-carboxylic Acid, a Diastereoselective Approach

      Ilona Bułyszko, Maria Chrzanowska, Agnieszka Grajewska and Maria D. Rozwadowska

      Article first published online: 27 NOV 2014 | DOI: 10.1002/ejoc.201403218

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      The total synthesis of (+)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline-1-carboxylic acid involves a combination of two synthetic strategies, that is, the Petasis synthesis of amino acids and the Pomeranz–Fritsch–Bobbitt synthesis of tetrahydroisoquinoline derivatives. Chiral aminoacetaldehyde acetals were used as building blocks and to direct the stereochemistry of this synthesis.

  3. Short Communications

    1. Reductive Etherification

      Stereoselective Synthesis of cis-2,6-Disubstituted Morpholines and 1,4-Oxathianes by Intramolecular Reductive Etherification of 1,5-Diketones

      Santosh J. Gharpure, Dandela Anuradha, Jonnalagadda V. K. Prasad and Pidugu Srinivasa Rao

      Article first published online: 26 NOV 2014 | DOI: 10.1002/ejoc.201403294

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      A simple and efficient, Lewis acid catalysed reductive etherification strategy for the stereoselective synthesis of cis-2,6-disubstituted morpholines and 1,4-oxathianes starting from readily available 1,5-diketones has been developed. The strategy is used in the total synthesis of morpholine-based natural product (±)-chelonin A and a formal total synthesis of (±)-chelonin C.

  4. Full Papers

    1. Dyes for Microscopy

      Functionalization of the meso-Phenyl Ring of Rhodamine Dyes Through SNAr with Sulfur Nucleophiles: Synthesis, Biophysical Characterizations, and Comprehensive NMR Analysis

      Gyuzel Yu. Mitronova, Svetlana Polyakova, Christian A. Wurm, Kirill Kolmakov, Thomas Wolfram, Dirk N. H. Meineke, Vladimir N. Belov, Michael John and Stefan W. Hell

      Article first published online: 26 NOV 2014 | DOI: 10.1002/ejoc.201403269

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      Aromatic nucleophilic substitution of fluorine in 9-(3′-carboxy-4′,5′,6′,7′-trifluorophenyl) groups of xanthene dyes is regioselective (for thiols and amines). The reaction was used for the synthesis of a “bright” and very photostable dye for two-color superresolution microscopy. Characteristics of the NMR spectra may be used for structure elucidation of other fluorescent dyes.

  5. Corrections

    1. You have free access to this content
  6. Full Papers

    1. Sensors

      Ratiometric Detection of Adenosine-5′-triphosphate (ATP) and Cytidine-5′-triphosphate (CTP) with a Fluorescent Spider-Like Receptor in Water

      Abhishek Kumar Gupta, Abhimanew Dhir and Chullikkattil P. Pradeep

      Article first published online: 26 NOV 2014 | DOI: 10.1002/ejoc.201403073

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      A series of water-soluble spider-like receptor molecules has been developed by the Schiff-base condensation of tris(hydroxymethyl)aminomethane (TRIS) with 2,6-diformylphenol (dfp) derivatives. The products could be used for selective fluorescent sensing of adenosine-5-triphosphate (ATP) and cytidine-5′-triphosphate (CTP) in 100 % aqueous media at pH 7.2.

    2. Thioacetal Cleavage

      An Organocatalytic Process for the Hydrolytic Cleavage of Dithianes Mediated by Imidazolium Ions: No Harsh Agents Required

      Lauren Myles, Nicholas Gathergood and Stephen J. Connon

      Article first published online: 26 NOV 2014 | DOI: 10.1002/ejoc.201402947

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      A new, organocatalytic approach to the hydrolytic deprotection of dithianes has been developed involving a low-toxicity imidazolium-ion-based catalyst in an aqueous medium.

    3. Peptide Self-Dimerization

      Synthesis of Tetrasubstituted Symmetrical Pyrazines from β-Keto γ-Amino Esters: A Mild Strategy for Self-Dimerization of Peptides

      Mothukuri Ganesh Kumar, Varsha J. Thombare, Rupal D. Bhaisare, Anindita Adak and Hosahudya N. Gopi

      Article first published online: 25 NOV 2014 | DOI: 10.1002/ejoc.201403237

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      A facile synthesis of highly symmetrical tetrasubstituted pyrazines through simple aerial oxidation of β-keto γ-esters derived from amino acids and peptides is reported.

    4. Energetic Materials

      Pentaerythritol-Based Energetic Materials Related to PETN

      Quirin J. Axthammer, Burkhard Krumm and Thomas M. Klapötke

      Article first published online: 25 NOV 2014 | DOI: 10.1002/ejoc.201403265

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      New tetravalent pentaerythritol tetranitrocarbamate (PETNC) and its tetraammonium salt have been synthesized by an efficient two-step synthesis starting from pentaerythritol, the precursor to pentaerythritol tetranitrate (PETN). Their energetic properties are discussed in comparison with PETN.

  7. Short Communications

    1. Superstable Palladium(0) Complex

      Superstable Palladium(0) Complex as an Air- and Thermostable Catalyst for Suzuki Coupling Reactions

      Alexandra Jakab, Zoltán Dalicsek, Tamás Holczbauer, Andrea Hamza, Imre Pápai, Zoltán Finta, Géza Timári and Tibor Soós

      Article first published online: 25 NOV 2014 | DOI: 10.1002/ejoc.201403214

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      An unprecedentedly thermo- and air-stable Pd0 complex from readily available electron-poor trifluoromethylated phosphine is reported. The stability of the complex is associated with unusually strong ligand–ligand noncovalent interactions. The unique stability of the complex and the presence of hydrophobic structural elements are exploited in catalytic Suzuki–Miyaura coupling reactions.

  8. Full Papers

    1. Fused Porphycenes

      Dibenzoporphycene – Platform for the Generation of Fused Porphycenes

      Wolfgang Brenner and Norbert Jux

      Article first published online: 25 NOV 2014 | DOI: 10.1002/ejoc.201403067

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      A fused porphycene is generated through a shortened synthetic route. This molecule will serve as a starting point for the synthesis of larger fused porphycenes.

    2. Ligand- and Base-Free CuII-Mediated Selective S-Arylation of α-Enolic Dithioesters by Chan–Lam Coupling at Room Temperature

      Suvajit Koley, Sushobhan Chowdhury, Tanmoy Chanda, B. Janaki Ramulu, Namrata Anand and Maya Shankar Singh

      Article first published online: 25 NOV 2014 | DOI: 10.1002/ejoc.201403171

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      Ligand- and base-free cross-coupling of arylboronic acids with α-enolic dithioesters mediated by Cu(OAc)2 has been achieved at room temperature under aerobic neutral conditions to yield unsymmetrical α-oxoketene S,S-acetals for the first time. Distinctive features of this novel approach embrace short reaction times (5 min), good yields and highly selective C=S functionalization in one pot.

    3. Carbohydrate Mimetics

      Preparation of Multivalent Carbohydrate Mimetics Based on Enantiopure 1,2-Oxazines by Sonogashira Coupling and Subsequent Reductive Ring-Opening

      Maja Kandziora and Hans-Ulrich Reissig

      Article first published online: 25 NOV 2014 | DOI: 10.1002/ejoc.201403186

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      Modular, flexible, efficient! A series of mono- to tetravalent carbohydrate mimetics with the D-talose configuration have been prepared based on an aminopyran building block. Glaser and Sonogashira coupling reactions were the crucial reactions, followed by reductive steps, either palladium-catalyzed hydrogenolyses or a combination of hydrogenolysis and samarium diiodide promoted reductions.

    4. Proline Derivatives

      Efficient Synthesis of cis-3-Substituted Prolines by Bidentate-Assisted Palladium Catalysis

      Ruokun Feng, Binjie Wang, Yue Liu, Zhanxiang Liu and Yuhong Zhang

      Article first published online: 25 NOV 2014 | DOI: 10.1002/ejoc.201403191

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      A highly effective protocol for the synthesis of C-3-substituted prolines has been developed. Pd-catalyzed C(sp3)–H activation is used for the straightforward functionalization of prolines. The use of an 8-aminoquinolinecarboxamide directing group allows direct arylation, alkenylation, and alkylation at the C-3 position of prolines in moderate to high yields with diverse iodo- or bromo precursors.

    5. Unusual Sugars

      Chemical Synthesis of 1-Deoxy-L-fructose and L-Sorbose Through Carbonyl Translocation

      Hsin-Pei Wu, Nai-Yun Hsu, Tai-Ni Lu and Che-Chien Chang

      Article first published online: 25 NOV 2014 | DOI: 10.1002/ejoc.201403196

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      Two rare sugars – 1-deoxy-L-fructose and L-sorbose – were synthesized from inexpensive starting materials by a carbonyl translocation method.

    6. Drug Conjugates

      Synthesis and Cytotoxic Activity of Self-Assembling Squalene Conjugates of 3-[(Pyrrol-2-yl)methylidene]-2,3-dihydro-1H-indol-2-one Anticancer Agents

      Eric Buchy, Sabrina Valetti, Simona Mura, Julie Mougin, Claire Troufflard, Patrick Couvreur and Didier Desmaële

      Article first published online: 21 NOV 2014 | DOI: 10.1002/ejoc.201403088

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      New squalene conjugates of antiangiogenic 3-(pyrrolyl)methylidenyl-substituted oxindoles sunitinib and semaxanib were synthesized. Strategies to link squalene to the oxindole nitrogen through a pH-sensitive linker are presented. These squalenoyl prodrugs self-assemble into nanoparticles of about 150 nm in size, and show notable cytotoxicity on the human umbilical vein endothelial cell line

  9. Short Communications

    1. Arylation

      Direct Arylation of Imidazo[1,5-a]azines Through Ruthenium and Palladium Catalysis

      Daniela Sustac Roman, Valentin Poiret, Guillaume Pelletier and André B. Charette

      Article first published online: 21 NOV 2014 | DOI: 10.1002/ejoc.201403268

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      The RuII-catalyzed direct ortho-arylation of C-3-substituted imidazo[1,5-a]azines with (hetero)aryl halides is investigated. Multiple arylations are performed sequentially in a one-pot procedure with the use of RuII and PdII catalysts.

  10. Full Papers

    1. Fluorescent Probes

      A Synthetic Route to 3-(Heteroaryl)-7-hydroxycoumarins Designed for Biosensing Applications

      Benoît Roubinet, Arnaud Chevalier, Pierre-Yves Renard and Anthony Romieu

      Article first published online: 21 NOV 2014 | DOI: 10.1002/ejoc.201403215

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      A condensation reaction between 7-acetoxy-3-formylcoumarin and various C- and/or N-monosubstituted ortho-phenylendiamine derivatives has led to a new class of 3-(heteroaryl)-7-hydroxycoumarins meeting the requirements for biosensing applications (bioconjugation ability, water solubility, and high “fluorogenic” reactivity).

    2. Macrocycles

      Multigram Four-Step Synthesis of 1,4,7-Triazacyclononanes with 2Ra/Rb N-Functionalization Pattern by Starting from Diethylenetriamine

      Guillaume Gros and Jens Hasserodt

      Article first published online: 21 NOV 2014 | DOI: 10.1002/ejoc.201402821

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      A four-step synthetic route to 1,4,7-triazacyclononanes with a 2Ra/Rb N-functionalization pattern is presented. The formation of the macrocycle is greatly facilitated by the use of an organic template. This allows for the atom-economic, multigram syntheses of several substituted derivatives with excellent overall yields in less than five days.

    3. Peptide Synthesis

      The Effect of Counterion and Tertiary Amine on the Efficiency of N-Triazinylammonium Sulfonates in Solution and Solid-Phase Peptide Synthesis

      Beata Kolesinska, Kamil K. Rozniakowski, Justyna Fraczyk, Inga Relich, Anna Maria Papini and Zbigniew J. Kaminski

      Article first published online: 21 NOV 2014 | DOI: 10.1002/ejoc.201402862

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      The structure of the counterion is important in peptide synthesis. Triazine-based sulfonates derived from three tertiary amines and four sulfonic acids with very diverse properties, which yield exactly the same “superactive” triazine ester after activation of the carboxylic function, presented significant differences in stability, tendency to epimerization, coupling rate, yield, and purity of the final products.

    4. Synthetic Methods

      Bis(trimethylsilyl)selenide in the Selective Synthesis of β-Hydroxy, β-Mercapto, and β-Amino Diorganyl Diselenides and Selenides Through Ring Opening of Strained Heterocycles

      Damiano Tanini, Alessandro Degl'Innocenti and Antonella Capperucci

      Article first published online: 21 NOV 2014 | DOI: 10.1002/ejoc.201403015

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      A selective approach to β-hydroxy, β-mercapto, and β-amino dialkyl diselenides and selenides is described through reaction of bis(trimethylsilyl)selenide (HMDSS) with epoxides, thiiranes, and aziridines under suitable reaction conditions. 77Se NMR chemical shifts were measured to verify the selective synthesis of diselenides and selenides.

    5. Peptide Antibiotics

      Synthesis of Mono and Bis[60]fullerene-Based Dicationic Peptoids

      Sreenu Jennepalli, Katherine A. Hammer, Thomas V. Riley, Stephen G. Pyne and Paul A. Keller

      Article first published online: 21 NOV 2014 | DOI: 10.1002/ejoc.201403046

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      [60]Fullerenyldihydropyrrole peptides were prepared from the coupling of mono and bis[60]fullerenyldihydropyrrolecarboxylic acids with peptides to produce a series of fullerenyl-anchored tetra- and penta-peptides. Their synthesis and characterisation are discussed in this paper.

  11. Short Communications

    1. Asymmetric Synthesis

      Chiral Auxiliary Induced Diastereoselective Synthesis of (R,R)-N,N′-Di(tert-butoxycarbonyl)cyclohex-4-ene-1,2-diamine

      Davide Balestri, Stefano Grilli, Ciro Romano and Diego Savoia

      Article first published online: 21 NOV 2014 | DOI: 10.1002/ejoc.201403058

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      (R,R)-N,N′-Di(tert-butoxycarbonyl)cyclohex-4-ene-1,2-diamine is synthesized from the glyoxal diimine, which is prepared by using a chiral auxiliary. Double allylation to the diimine proceeds with excellent diastereoselectivity; then, removal of the N-substituents followed by ring-closing metathesis (RCM) of the diene moiety affords the protected cyclohex-4-ene-1,3-diamine in satisfactory overall yield.

  12. Full Papers

    1. Halo Oxime Ethers

      A General Metal-Assisted Synthesis of α-Halo Oxime Ethers from Nitronates and Nitro Compounds

      Alexey Yu. Sukhorukov, Maria A. Kapatsyna, Tammy Lim Ting Yi, Hyeong Ryool Park, Yana A. Naumovich, Petr A. Zhmurov, Yulia A. Khomutova, Sema L. Ioffe and Vladimir A. Tartakovsky

      Article first published online: 19 NOV 2014 | DOI: 10.1002/ejoc.201403083

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      A general approach to the synthesis of α-halo oxime ethers is reported. The strategy involves as a key step an unprecedented reaction of readily accessible bis(oxy)enamines with a metal halide that acts both as a promoter and halide source. A variety of cyclic and acyclic ethers of α-halo oximes have been synthesized in good-to-high yields.

    2. Carbonylation

      Synthesis of Vinyl- and Aryl–Acyl Sulfonimidamides Through Pd-Catalyzed Carb­onylation Using Mo(CO)6 as ex situ CO Source

      Prasad B. Wakchaure, Sanjay R. Borhade, Anja Sandström and Per I. Arvidsson

      Article first published online: 19 NOV 2014 | DOI: 10.1002/ejoc.201403148

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      N-(α,β-Unsaturated acyl) sulfonimidamides have been prepared through a Pd-catalyzed carbonylation protocol, employing sulfonimidamide nucleophiles, CO gas released ex situ, and vinyl/aryl halides and triflates as reagents. The obtained products undergo facile thermolytic Boc deprotection in DMSO, thereby offering convenient access to deprotected analogues.

  13. Microreviews

    1. Pd in Natural Product Synthesis

      Palladium-Catalyzed α-Arylation Reactions in Total Synthesis

      Sudheesh T. Sivanandan, Ashna Shaji, Ibrahim Ibnusaud, Carin C. C. Johansson Seechurn and Thomas J. Colacot

      Article first published online: 19 NOV 2014 | DOI: 10.1002/ejoc.201403301

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      Metal-catalyzed α-arylation of carbonyl compounds has become a powerful tool for organic chemists to construct carbon-carbon bonds through C–H functionalization based on enolization. This microreview highlights recent applications of α-arylation in total syntheses both of natural products and of active pharmaceutical ingredients (APIs).

  14. Short Communications

    1. Organocatalysis

      Enantioselective Epoxidation of Dihydroquinolines by Using Iminium Salt Organo­catalysts

      Philip C. Bulman Page, David P. Day and Yohan Chan

      Article first published online: 19 NOV 2014 | DOI: 10.1002/ejoc.201403132

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      The first examples of asymmetric epoxidation of dihydroquinoline substrates by using iminium salt organocatalysts are reported. The 3,4-epoxytetrahydroquinoline products are obtained with moderate to good enantioselectivities.

  15. Full Papers

    1. Intramolecular [4+2] Cycloaddition

      Synthesis of Phenanthridine Derivatives Functionalized in the C-Ring by Means of IMDAF Reactions under Microwave or Conventional Heating Conditions

      Håkon Sætren Gulbrandsen, Martin Hennum, Maksim Osheka, Matthew Lovell Read and Lise-Lotte Gundersen

      Article first published online: 18 NOV 2014 | DOI: 10.1002/ejoc.201403111

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      Phenanthridines functionalized in the C-ring have been synthesized by IMDAF cyclization of ortho-furyl(alkenylamino)arenes. The outcomes of the reactions are highly dependent on the substitution patterns on both the dienophile and the arene components, as well as on the reaction conditions.

    2. Peptoid Monomer Synthesis

      N-Substituted Glycines with Functional Side-Chains for Peptoid Synthesis

      Adeline René, Jean Martinez and Florine Cavelier

      Article first published online: 18 NOV 2014 | DOI: 10.1002/ejoc.201402864

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      N-Substituted glycines (NSG) constitute mimics of natural amino acids that are used in peptoid synthesis. We developed a method to synthesize NSG bearing reactive secondary heterofunctionality. Persilylation was used as temporary protection, and analogues of serine, cysteine, tyrosine and tryptophan were prepared. N-Homotyrosine (N-hTyr) has been introduced into a peptide sequence of interest.

    3. Organocatalysis

      Organocatalytic Domino Michael–Heterocyclization Reaction of α,β-Unsaturated Aldehydes and α-Cyano Ketones: Synthesis of Enantioenriched 4,5,6-Trisubstituted 3,4-Dihydropyranones

      James O. Guevara-Pulido, José M. Andrés and Rafael Pedrosa

      Article first published online: 17 NOV 2014 | DOI: 10.1002/ejoc.201402982

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      One-pot domino enantioselective organocatalytic Michael-addition–heterocyclization followed by oxidation of the hemiacetal intermediate allows the synthesis of enantioenriched 3,4-dihydropyranone derivatives.

    4. Organometallic Addition

      Addition of Vinylmetallic Reagents to Chiral 2-Formyltetrahydrofuran

      Janire Lamariano-Merketegi, Adriana Lorente, Alejandro Gil, Fernando Albericio and Mercedes Álvarez

      Article first published online: 17 NOV 2014 | DOI: 10.1002/ejoc.201402987

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      A chelation-controlled addition, a carboalumination, and a Nozaki–Hiyama–Kishi (NHK) reaction were used to study the stereoselective addition of vinylmetallic reagents to enantiopure trisubstituted 2-formyl-tetrahydrofuran compounds. The optimal conditions for the carboalumination and NHK reactions provided satisfactory yields and diastereoselectivities.

    5. Direct Arylation Method

      You have full text access to this OnlineOpen article
      Direct Arylation of Benzo[b]furan and Other Benzo-Fused Heterocycles

      Toan Dao-Huy, Maximilian Haider, Fabian Glatz, Michael Schnürch and Marko D. Mihovilovic

      Article first published online: 17 NOV 2014 | DOI: 10.1002/ejoc.201403125

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      The direct arylation of benzo-fused heterocycles is reported. A common strategy could be applied to benzofuran, benzothiophene, and indole with good selectivity for arylation at the 2-position. In addition, the same method could be applied to the arylation at C3 in a second C–H activation step.

    6. Halocyclization of Alkynes

      Synthesis of Halo-Enol Phostones by Using DMAP-Catalyzed Halocyclization of Alkynylphosphonic Monoesters

      Jiale Huang, Haiyang Wang and Ai-Yun Peng

      Article first published online: 17 NOV 2014 | DOI: 10.1002/ejoc.201403135

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      A series of non-benzo halo-enol phostones were synthesized by using a DMAP-catalyzed [DMAP = 4-(dimethylamino)pyridine] halocyclization of 4-pentynylphosphonic monoesters with N-bromosuccinimide or N-iodosuccinimide in CHCl3. The reaction showed high regioselectivity for six-membered ring products, but no stereoselectivity was observed. The (Z) and (E) stereoisomers were isolated in each case.

    7. Thieno-aza-acenes

      Dithienoquinazolines – A Convenient Synthesis by the Oxidative Photocyclization of 4,5-Dithienyl-Substituted Pyrimidines and Their Photophysical Properties

      Egor V. Verbitskiy, Pavel A. Slepukhin, Marina S. Valova, Ekaterina M. Cheprakova, Akesandr V. Schepochkin, Gennady L. Rusinov and Valery N. Charushin

      Article first published online: 17 NOV 2014 | DOI: 10.1002/ejoc.201403212

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      A convenient route to a new class of thienoacene systems bearing a fused pyrimidine ring is presented along with their optoelectronic properties. The photophysical and electrochemical properties of these newly developed thieno-aza-acenes have been investigated by UV/Vis absorption and photoluminescence spectrophotometry and cyclic voltammetry, and some crystal structures have also been determined.

    8. C–H Bond Functionalization

      Iron-Catalyzed C–H Bond Functionalization for the Exclusive Synthesis of Pyrido[1,2-a]indoles or Triarylmethanols

      Iyyanar Karthikeyan and Govindasamy Sekar

      Article first published online: 17 NOV 2014 | DOI: 10.1002/ejoc.201403233

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      An efficient iron-catalyzed C–H bond functionalization that proceeded through an intramolecular C–H amination reaction under nitrogen was employed for the synthesis of pyrido[1,2-a]indoles from 2-benzhydrylpyridines. Under oxygen, the same 2-benzhydrylpyridines were used for the synthesis of the corresponding tertiary alcohols. Overall, a change of atmosphere altered the course of the reaction.

  16. Microreviews

    1. Asymmetric Organocatalysis

      Isohexides as Versatile Scaffolds for Asymmetric Catalysis

      Mohammed Kadraoui, Thibault Maunoury, Zoubir Derriche, Stéphane Guillarme and Christine Saluzzo

      Article first published online: 17 NOV 2014 | DOI: 10.1002/ejoc.201402851

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      Two series of dianhydrohexitol derivatives, the first preserving the original bis-fused THF backbones and the second originating from single THF ring-opening reactions, are used as asymmetric ligands in organometallic catalysis or as asymmetric organocatalysts. Their synthesis and their application in different asymmetric reactions for the formation of C–H, C–C, C–N, and C–S bonds are discussed.

  17. Short Communications

    1. Multicomponent Reactions

      Concise Synthesis of Tetrazole–Ketopiperazines by Two Consecutive Ugi Reactions

      Tryfon Zarganes-Tzitzikas, Pravin Patil, Kareem Khoury, Eberhardt Herdtweck and Alexander Dömling

      Article first published online: 17 NOV 2014 | DOI: 10.1002/ejoc.201403401

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      A novel compound class of tetrazole–diketopiperazines is described. Two multicomponent reactions are used during the synthesis: the Ugi tetrazole four-component reaction (4CR) and the classical intramolecular Ugi 4CR. Tetrazole–diketopiperazines comprise analogs of and are bioisosteric to bioactive diketopiperazines. The scaffold is currently produced to fill the screening deck of the European Lead Factory.

  18. Full Papers

    1. Corrole Synthesis

      Synthesis and Characterization of cis-A2B-Type meso-Triaryl-Substituted Corroles

      Shota Ooi, Takayuki Tanaka and Atsuhiro Osuka

      Article first published online: 14 NOV 2014 | DOI: 10.1002/ejoc.201403217

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      A rational synthesis of cis-A2B-type corroles through a [2+2] approach has been developed, which allowed the synthesis of six new corroles in moderate yields. These corroles were structurally well-characterized and their optical and electrochemical properties were also studied.

    2. Persistent Radicals

      Tetrathiatriarylmethyl Radicals Conjugated to an RGD-Peptidomimetic

      Benoît Driesschaert, Philippe Levêque, Bernard Gallez and Jacqueline Marchand-Brynaert

      Article first published online: 14 NOV 2014 | DOI: 10.1002/ejoc.201403049

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      Tetrathiatriarylmethyl (TAM) radicals are favourite spin labels for electron paramagnetic resonance imaging. In this work, we report a straightforward synthesis of new TAM radicals bound to an RGD-peptidomimetic. These new radicals are stable in solution, and sensitive to oxygen, and their experimental EPR data is consistent with DFT calculations.

    3. Marine Natural Products

      A Versatile Total Synthesis of Trachycladines A and B and Their Analogues

      Zisis V. Peitsinis, Dafni A. Melidou, John G. Stefanakis, Helen Evgenidou and Alexandros E. Koumbis

      Article first published online: 14 NOV 2014 | DOI: 10.1002/ejoc.201403091

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      Marine nucleosides trachycladines A and B were synthesized from D-ribose, using a versatile and high-yielding scheme. The same approach was followed to prepare two analogues.

  19. Short Communications

    1. Natural Products

      Facile Synthesis of Cyclohexanediones and Dialkylresorcinols – Bioactive Natural Products from Entomopathogenic Bacteria

      Max Kronenwerth, Christina Dauth, Marcel Kaiser, Iain Pemberton and Helge B. Bode

      Article first published online: 13 NOV 2014 | DOI: 10.1002/ejoc.201403346

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      Synthesis following biosynthesis: A facile synthesis route to dialkylresorcinols and cyclohexanediones is developed that briefly follows the biosynthesis pathways of these widespread natural product classes.

  20. Full Papers

    1. Gold Catalysts

      Ammonium-Salt-Tagged IMesAuCl Complexes and Their Application in Gold-Catalyzed Cycloisomerization Reactions in Water

      Katrin Belger and Norbert Krause

      Article first published online: 12 NOV 2014 | DOI: 10.1002/ejoc.201403153

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      The total synthesis of water-soluble ammonium-salt-tagged NHC–gold complexes is described, as well as their application in aqueous media and their recyclability.

    2. Donor–Acceptor Systems

      Systematic Variation of Cyanobuta-1,3-dienes and Expanded Tetracyanoquinodimethane Analogues as Electron Acceptors in Photoactive, Rigid Porphyrin Conjugates

      Lorenz M. Urner, Michael Sekita, Nils Trapp, W. Bernd Schweizer, Michael Wörle, Jean-Paul Gisselbrecht, Corinne Boudon, Dirk M. Guldi and François Diederich

      Article first published online: 12 NOV 2014 | DOI: 10.1002/ejoc.201403252

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      The modular synthesis and characterization of a series of rigid ZnII porphyrin conjugates is described. The push–pull chromophores incorporated as electron acceptors feature first reduction potentials ranging from –1.78 to –0.58 V vs. Fc+/Fc, and affect the extent of ZnII porphyrin fluorescence quenching according to their acceptor strength.

  21. Short Communications

    1. Enediones

      Synthesis of (E)-1,4-Enediones from α-Halo Ketones Through a Sodium Sulfinate Mediated Reaction

      Su-Yi Li, Xiao-Bing Wang, Neng Jiang and Ling-Yi Kong

      Article first published online: 12 NOV 2014 | DOI: 10.1002/ejoc.201403236

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      A mild and practical protocol for the synthesis of 1,4-enedione from α-halo ketones through a sodium sulfinate mediated reaction is reported. This reaction enables the construction of symmetric and unsymmetric 1,4-enediones with complete E selectivity.

    2. Asymmetric Alkylation

      Catalytic Asymmetric Alkylation of Aryl Heteroaryl Ketones

      Pablo Ortiz, Ana M. del Hoyo and Syuzanna R. Harutyunyan

      Article first published online: 12 NOV 2014 | DOI: 10.1002/ejoc.201403297

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      The first example of the direct catalytic asymmetric alkylation of diaryl ketones by using Grignard reagents is reported. The low reactivity and similarity of the enantiotopic faces of the substrates is partially overcome, which results in the corresponding enantioenriched diarylmethanol core.

    3. Deoxygenation

      Light-Mediated Deoxygenation of Alcohols with a Dimeric Gold Catalyst

      Terry McCallum, Ekaterina Slavko, Mathieu Morin and Louis Barriault

      Article first published online: 12 NOV 2014 | DOI: 10.1002/ejoc.201403351

      Thumbnail image of graphical abstract

      While exploring orthogonal reactivity with [Au2(dppm)2]Cl2 [dppm = 1,1-bis(diphenylphosphino)methane], the high-yielding photochemical bromination of alcohols was found. The simplicity of this reaction makes it a perfect match for combining bromination with reductive dehalogenation through photoredox catalysis. The highly efficient one-pot reductive deoxygenation protocol for primary alcohols is presented.

    4. Cyclopropanation

      Palladium-Catalyzed Cyclopropanation of Strained Alkenes with 3-Pinacolatoboryl-1-arylallyl Carboxylates

      Yoshikazu Horino, Yu Takahashi, Ryota Kobayashi and Hitoshi Abe

      Article first published online: 10 NOV 2014 | DOI: 10.1002/ejoc.201403284

      Thumbnail image of graphical abstract

      The palladium-catalyzed cyclopropanation of strained alkenes with 3-pinacolatoboryl-1-arylallyl carboxylates is described. The reaction proceeds smoothly under mild conditions, and the cyclopropanation products are obtained in good to high yields with high diastereoselectivities if CsF, 18-crown-6, and molecular sieves are used as additives.

    5. Phase-Transfer Catalysis

      Cyclopeptoids as Phase-Transfer Catalysts for the Enantioselective Synthesis of α-Amino Acids

      Rosaria Schettini, Brunello Nardone, Francesco De Riccardis, Giorgio Della Sala and Irene Izzo

      Article first published online: 10 NOV 2014 | DOI: 10.1002/ejoc.201403224

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      Cyclopeptoids are a novel class of efficient and tunable chiral macrocyclic phase-transfer catalyts. Screening of catalysts for the enantioselective alkylation of N-(diphenylmethylene)glycine tert-butyl ester shows the crucial role of N-arylmethyl residues.

    6. Catalyst Immobilization

      Immobilization of an Anthracene-Tagged Ruthenium Complex on a 2,4,7-Trinitrofluoren-9-one-Grafted Silica: Efficiency and Recyclability in Olefin Metathesis Reactions

      Houssein Nasrallah, Anastassiya Pagnoux, Dorian Didier, Caroline Magnier, Loïc Toupet, Régis Guillot, Christophe Crévisy, Marc Mauduit and Emmanuelle Schulz

      Article first published online: 10 NOV 2014 | DOI: 10.1002/ejoc.201403194

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      An anthracene group is linked to the N-heterocyclic carbene moiety of a M71-SIPr-type Ru complex. The tagged complex thus obtained is immobilized by charge-transfer interactions to a 2,4,7-trinitrofluoren-9-one-grafted passivated silica. The immobilized complex is an efficient olefin metathesis catalyst and can be reused five times in a multisubstrate olefin metathesis procedure.

    7. Metal-Free Iodination

      Transition-Metal-Free Oxidative Iodination of 1,3,4-Oxadiazoles

      Carl Albrecht Dannenberg, Vincent Bizet, Liang-Hua Zou and Carsten Bolm

      Article first published online: 6 NOV 2014 | DOI: 10.1002/ejoc.201403352

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      The transition-metal-free oxidative iodination of 2-substituted 1,3,4-oxadiazoles is developed to provide products in moderate to good yields with NaI as the halogen source and Selectfluor as the oxidant. Neither anhydrous conditions nor an inert atmosphere is required, which renders this process synthetically attractive.

  22. Corrections

    1. You have free access to this content
      Application of the Palladium-Catalysed Norbornene-Assisted Catellani Reaction Towards the Total Synthesis of (+)-Linoxepin and Isolinoxepin

      Zafar Qureshi, Harald Weinstabl, Marcel Suhartono, Hongqiang Liu, Pierre Thesmar and Mark Lautens

      Article first published online: 6 NOV 2014 | DOI: 10.1002/ejoc.201403388

      This article corrects:
  23. Short Communications

    1. C–H Activation

      Room-Temperature Direct Alkenylation of 3-Arylsydnones

      Yiwen Yang and Chunxiang Kuang

      Article first published online: 6 NOV 2014 | DOI: 10.1002/ejoc.201403211

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      A new efficient method for the direct alkenylation of 3-arylsydnones by palladium-catalyzed C–H functionalization is developed. The reaction proceeds smoothly at room temperature and delivers the products in yields up to 83 %.

    2. Asymmetric Epoxidation

      Iron(II)-Catalyzed Asymmetric Epoxidation of Trisubstituted α,β-Unsaturated Esters

      Lan Luo and Hisashi Yamamoto

      Article first published online: 6 NOV 2014 | DOI: 10.1002/ejoc.201403220

      Thumbnail image of graphical abstract

      The asymmetric epoxidation of trisubstituted α,β-unsaturated esters is described. The oxidation utilizes a pseudo-C2-symmetric iron(II) catalyst [Fe(L*)2(CH3CN)(OTf)](OTf) (Tf = trifluoromethylsulfonyl) and peracetic acid as the oxidant and yields α,β-epoxy esters with high enantiomeric purity (up to 99 % ee).

  24. Full Papers

    1. Carbohydrates

      Stereoselective Synthesis of C-2-Methylene and C-2-Methyl α- and β-C-Glycosides from 2-C-Branched Glycals: Formal Total Synthesis of (–)-Brevisamide

      Chalapala Sudharani, Patteti Venukumar and Perali Ramu Sridhar

      Article first published online: 6 NOV 2014 | DOI: 10.1002/ejoc.201403062

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      The Claisen rearrangement of the deoxysugar-derived 2-vinyloxymethyl glycal derivatives led to the stereoselective formation of C-2-methylene-α-C-glycosides, which were converted into the corresponding C-2-methylene-β-C-glycosides through an epimerization reaction. The developed method was successfully applied to the formal total synthesis of (–)-brevisamide.

  25. Short Communications

    1. Total Synthesis

      Total Synthesis of (±)-Oxalicumone C and Chiral Resolution and Elucidation of Its Absolute Configuration

      Christoph Wink, Lars Andernach, Till Opatz and Siegfried R. Waldvogel

      Article first published online: 6 NOV 2014 | DOI: 10.1002/ejoc.201403189

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      We present the first racemic total synthesis of oxalicumone C. After resolution, the absolute configuration of the naturally occurring enantiomer is assigned by comparison of the experimental and calculated vibrational and electronic circular dichroism spectra. The results show that the naturally occurring product has the (S) configuration.

  26. Full Papers

    1. Fluorophores

      Rapid Synthesis of Unsymmetrical Sulforhodamines Through Nucleophilic Amination of a Monobrominated Sulfoxanthene Dye

      Arnaud Chevalier, Kevin Renault, Frédéric Boschetti, Pierre-Yves Renard and Anthony Romieu

      Article first published online: 5 NOV 2014 | DOI: 10.1002/ejoc.201403165

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      Simplicity and diversity! A range of primary and secondary functionalized amines were easily introduced onto a sulfoxanthene dye through simple metal-free SNAr reactions to provide original sulforhodamine fluorophores with promising properties.

    2. Polymeric Zwitterions

      A Synthetic Route to Sulfobetaine Methacrylates with Varying Charge Distance

      Domenic Kratzer, Leonie Barner, Christian Friedmann, Stefan Bräse and Joerg Lahann

      Article first published online: 5 NOV 2014 | DOI: 10.1002/ejoc.201402734

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      A simple and highly universal three-step procedure has been developed for the synthesis of sulfobetaine methacrylates with variation of the charge separation distance. The protocol provides access to a library of new zwitterionic precursors that have potential for a range of applications in polymer chemistry and materials science.

    3. Cycloaddition Reactions

      The First Bidirectional [4+2] Cycloadditions of Benzo[1,2:4,5]dicyclobutenes: Synthesis of Benzo[1,2-f:4,5-f′]diisoindole-1,3,7,9-tetraones

      Ismail Abdelshafy Abdelhamid and Holger Butenschön

      Article first published online: 5 NOV 2014 | DOI: 10.1002/ejoc.201403247

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      A bidirectional sequence of electrocyclic ring opening, [4+2] cycloaddition, methanol elimination, and dehydrogenation allows the formation of benzo[1,2-f:4,5-f′]diisoindole-1,3,7,9-tetraones from benzo[1,2:4,5]dicyclobutenes.

  27. Short Communications

    1. Oxidative Cyanation

      Practical Access to Aromatic Thiocyanates by CuCN-Mediated Direct Aerobic Oxidative Cyanation of Thiophenols and Diaryl Disulfides

      Thomas Castanheiro, Mihaela Gulea, Morgan Donnard and Jean Suffert

      Article first published online: 5 NOV 2014 | DOI: 10.1002/ejoc.201403279

      Thumbnail image of graphical abstract

      A practical and mild aerobic oxidative CuCN-mediated cyanation of thiophenols and diaryl disulfides is reported. The reaction is performed in air at room temperature and reaches aromatic thiocyanates in moderate to good yields starting from a broad range of diversely functionalized substrates. TMEDA = N,N,N′,N′-tetramethyl-1,2-ethylenediamine.

    2. Decarboxylative Methylthiolation

      Palladium-Catalyzed Decarboxylative Methylthiolation of Aromatic Carboxylic Acids by Using DMSO as the Sulfurizing Reagent

      Zhengjiang Fu, Zhaojie Li, Qiheng Xiong and Hu Cai

      Article first published online: 31 OCT 2014 | DOI: 10.1002/ejoc.201403147

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      Aryl methyl thioethers are synthesized by the Pd-catalyzed decarboxylation of aromatic carboxylic acids with DMSO. Simple and readily available starting materials, excellent functional group tolerance, high selectivities, and moderate to good yields provide this efficient and practical protocol with a broad utility in organic synthesis.

  28. Full Papers

    1. Total Synthesis

      Protecting-Group-Free Diastereoselective Total Synthesis of (±)-6-epi-Cleistenolide and Chemoenzymatic Synthesis of (–)-6-epi-Cleistenolide

      Pankaj S. Mahajan, Rajesh G. Gonnade and Santosh B. Mhaske

      Article first published online: 31 OCT 2014 | DOI: 10.1002/ejoc.201403123

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      A short, efficient, practical, and protecting-group-free diastereoselective total synthesis of 6-epi-(±)-cleistenolide (1) has been achieved in five steps in 60 % overall yield. The use of a chemoenzymatic approach also gave (–)-6-epi-cleistenolide (1) with >99.9 % ee.

    2. Gene Delivery

      Cationic Trialkylphosphates: Synthesis and Transfection Efficacies Compared to Phosphoramidate Analogues

      Stéphanie S. Le Corre, Mathieu Berchel, Tony Le Gall, Jean-Pierre Haelters, Pierre Lehn, Tristan Montier and Paul-Alain Jaffrès

      Article first published online: 31 OCT 2014 | DOI: 10.1002/ejoc.201403103

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      Cationic symmetric and nonsymmetric trialkylphosphates were synthesised. These vectors were evaluated for gene delivery in four human-derived cell lines and compared to their equivalent lipophosphoramidates.

  29. Short Communications

    1. C–H Activation

      A Robust and Efficient Catalyst Possessing an Electron-Deficient Ligand for the Palladium-Catalyzed Direct Arylation of Heteroarenes

      Alexandra Jakab, Zoltán Dalicsek and Tibor Soós

      Article first published online: 31 OCT 2014 | DOI: 10.1002/ejoc.201402586

      Thumbnail image of graphical abstract

      Application of a unique, thermally stable, and air-stable Pd0 catalyst for the direct arylation of heteroarenes is described. The combination of only 0.5–2 mol-% of the Pd0 complex possessing an electron-deficient fluorinated phosphine ligand with a substoichiometric quantity of pivalic acid (PivOH) generates an efficient system to promote the C–H activation of a broad range of heteroarenes.

  30. Full Papers

    1. Asymmetric Synthesis

      Asymmetric Synthesis of 3,4-Disubstituted Proline Derivatives: Application in Synthesis of Hepatitis C Virus Protease Inhibitor Telaprevir

      Fan Zhang, Xiaoan Wen, Qing-Long Xu and Hongbin Sun

      Article first published online: 31 OCT 2014 | DOI: 10.1002/ejoc.201403069

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      Asymmetric synthesis of 3,4-disubstituted proline derivatives was developed through asymmetric ring opening of substituted anhydrides, intramolecular Strecker reaction, and thermodynamically controlled cyanide hydrolysis with high stereoselectivity and moderate yield. HCV protease inhibitor Telaprevir was synthesized by using the above methodology.

    2. Copper-Catalyzed C–H Coupling

      Copper-Catalyzed Regioselective Cross-Dehydrogenative Coupling of Coumarins with Benzylic Csp3–H Bonds

      Shi-Liu Zhou, Li-Na Guo and Xin-Hua Duan

      Article first published online: 31 OCT 2014 | DOI: 10.1002/ejoc.201403068

      Thumbnail image of graphical abstract

      An efficient copper-catalyzed regioselective dehydrogenative benzylation of coumarins has been developed. Both the quinolinones and naphthoquinones are also suitable substrates for this transformation. More importantly, the excellent selectivity of the reaction could be controlled by using a series of unactivated Csp3–H bonds.

    3. Fungal Natural Products

      Biosynthetically Distinct Cytotoxic Polyketides from Setophoma terrestris

      Tamam El-Elimat, Mario Figueroa, Huzefa A. Raja, Tyler N. Graf, Steven M. Swanson, Joseph O. Falkinham III, Mansukh C. Wani, Cedric J. Pearce and Nicholas H. Oberlies

      Article first published online: 31 OCT 2014 | DOI: 10.1002/ejoc.201402984

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      Sixteen polyketides, six of them new, were isolated from a fungal culture (Setophoma terrestris). Cytotoxicity assays were used to develop structure–activity relationships amongst the series.

    4. C–H Functionalization

      Iron(III)-Catalyzed C–H Functionalization: ortho-Benzoyloxylation of N,N-Dialkylanilines and Its Application to 1,4-Benzoxazepines

      Barreddi Chiranjeevi, Botla Vinayak, Thupakula Parsharamulu, Vemulapalli S. PhaniBabu, Bharatam Jagadeesh, Balasubramanian Sridhar and Malapaka Chandrasekharam

      Article first published online: 30 OCT 2014 | DOI: 10.1002/ejoc.201402751

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      An iron-catalyzed C–O bond-formation reaction that proceeds through C–H functionalization of N,N-dialkylanilines at the ortho-position is presented. The reaction is carried out under extremely mild conditions. The methodology has been successfully employed for the generation of 1,4-benzoxazepines and o-aminophenols.

    5. Natural Products

      Synthetic Strategies for the Synthesis and Transformation of Substituted Pyrrolinones as Advanced Intermediates for Rhazinilam Analogues

      Inga Kholod, Olivier Vallat, Ana-Maria Buciumas, Antonia Neels and Reinhard Neier

      Article first published online: 30 OCT 2014 | DOI: 10.1002/ejoc.201402903

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      An efficient sequence that proceeds through the crossed Mukaiyama aldol reaction, Staudinger reaction, and hydroxy elimination has been developed for the syntheses of substituted 3-pyrrolin-2-ones. This transformation has been used as a key step in the preparation of precursors containing all the atoms necessary for the construction of rings A, B, and C of rhazinilam analogues.

    6. Macrocyclic Chemistry

      Construction and Multiple Exterior Surface Functionalization of Giant Molecular Cages

      Muhammad Moazzam Naseer, De-Xian Wang, Liang Zhao and Mei-Xiang Wang

      Article first published online: 30 OCT 2014 | DOI: 10.1002/ejoc.201402963

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      Giant cage molecules with D3h- and C3v-symmetric triangular prism shapes are synthesized by a one-pot reaction method through a stepwise fragment-coupling approach. Multiple functionalizations on the cage surface with hydroxy, 2-pyridyl, and allyl groups have been implemented by aromatic nucleophilic substitution reactions of chlorotriazine with amines or aliphatic substitution reactions.

    7. Nitrogen Heterocycles

      Rhodium(III)-Catalyzed One-Pot Access to Isoquinolines and Heterocycle-Fused Pyridines in Aqueous Medium through C–H Cleavage

      Jitan Zhang, Hongsheng Qian, Zhanxiang Liu, Chunhua Xiong and Yuhong Zhang

      Article first published online: 30 OCT 2014 | DOI: 10.1002/ejoc.201403085

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      An efficient RhIII-catalyzed ortho-C–H bond activation for the synthesis of substituted isoquinolines and heterocycle-fused pyridines in aqueous medium has been developed. This method involves the in situ generation of ketimines from ketones and ammonium acetate and subsequent oxidative C–H bond activation/annulation of the ketimines with alkynes to form the C–C/C–N bonds spontaneously.

    8. Triazoles

      Synthesis and NMR Analysis of 1,4-Disubstituted 1,2,3-Triazoles Tethered to Pyridine, Pyrimidine, and Pyrazine Rings

      Aljoša Bolje, Damijana Urankar and Janez Košmrlj

      Article first published online: 30 OCT 2014 | DOI: 10.1002/ejoc.201403100

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      Isomeric 1,4-disubstituted 1,2,3-triazoles functionalized with pyridine, pyrimidine, and pyrazine groups were prepared by a copper(I)-catalysed azide–alkyne cycloaddition reaction, and analysed by 1H–15N gs-HMBC NMR spectroscopy.

  31. Short Communications

    1. Asymmetric Catalysis

      Syntheses of Chiral Ferrocenophanes and Their Application to Asymmetric Catalysis

      Qiying Zhang, Xiuling Cui, Lianmei Chen, Haitao Liu and Yangjie Wu

      Article first published online: 30 OCT 2014 | DOI: 10.1002/ejoc.201402985

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      The synthesis of ferrocenophane–amines is developed. Compound L1 can be used as a ligand in the the copper-catalyzed oxidative coupling of 3-hydroxy-2-naphthoate to give the product in good yield with up to 92 % ee, and it also efficiently catalyzes the asymmetric Michael addition reaction as an organocatalyst.

    2. Mitsunobu Reagents

      Nonsymmetrical Azocarbonamide Carboxylates as Effective Mitsunobu Reagents

      Daniel P. Furkert, Benjamin Breitenbach, Ludovic Juen, Ina Sroka, Mathilde Pantin and Margaret A. Brimble

      Article first published online: 29 OCT 2014 | DOI: 10.1002/ejoc.201403152

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      A series of nonsymmetrical Mitsunobu reagents that avoid byproduct separation problems in this useful reaction are reported. They are readily prepared by a one-pot sequence from inexpensive, commercially available materials and are shown to possess activity that is parallel to that of diethyl azodicarboxylate/diisopropyl azodicarboxylate in a wide range of synthetic transformations.

  32. Full Papers

    1. Conjugation Effects

      Comparison of Linear and Cross-Conjugation from Rates of Vinylheptafulvene Ring-Closure

      Kasper Fjelbye, Trine Nørgaard Christensen, Martyn Jevric, Søren Lindbæk Broman, Anne Ugleholdt Petersen, Anders Kadziola and Mogens Brøndsted Nielsen

      Article first published online: 29 OCT 2014 | DOI: 10.1002/ejoc.201403117

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      The rate of electrocyclic ring-closure of vinylheptafulvene (VHF) to dihydroazulene (DHA) has been studied for a series of compounds bearing a rate-enhancing nitrophenyl group connected to the VHF through either a linear or cross-conjugated bridge. The photoactive DHA compounds were prepared by metal-catalyzed coupling reactions and converted into the VHFs by irradiation.

    2. Stereoselective Synthesis

      Stereoselective Synthesis of α-Trifluoromethyl Enones by AuI/CuI-Co-Catalyzed Tandem 1,3-Acyloxy Migration/Trifluoromethylation Reaction of Propargyl Acetates

      Yun-Long Ji, Jin-Hong Lin, Ji-Chang Xiao and Yu-Cheng Gu

      Article first published online: 29 OCT 2014 | DOI: 10.1002/ejoc.201403115

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      Under a co-catalytic AuI/CuI system, tandem 1,3-acyloxy migration/trifluoromethylation reactions of propargyl esters give α-trifluoromethyl enones with excellent stereoselectivity and in moderate yields.

    3. Asymmetric Synthesis

      Stereocontrolled Construction of the 3,4-Dihydrothiacarbazol-2(9H)-one Skeleton by Using Bifunctional Squaramide-Catalyzed Cascade Reactions

      Shanren Chen, Jianping Pan, Youming Wang and Zhenghong Zhou

      Article first published online: 29 OCT 2014 | DOI: 10.1002/ejoc.201403078

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      An efficient process for the enantioselective synthesis of optically active 3,4-dihydrothiacarbazol-2(9H)-one derivatives has been developed The cascade Michael addition/thiolysis reactions of 9-methylindoline-2-thiones and N-alkenoylphthalimides were promoted by a chiral bifunctional squaramide catalyst to give the desired products in acceptable yields with 54–98 % ee.

    4. Fullerene Functionalisation

      Reactivity of [60]Fullerene with Primary Nitro Compounds: Addition or Catalysed Condensation to Isoxazolo[60]fullerenes

      Giacomo Biagiotti, Stefano Cicchi, Francesco De Sarlo and Fabrizio Machetti

      Article first published online: 29 OCT 2014 | DOI: 10.1002/ejoc.201402990

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      Isoxazolino[60]fullerenes have been synthesised directly from activated nitro compounds by a catalytic process (DABCO or NMP/[Cu]). The protocol is simple, versatile and tolerant towards diverse functional groups. A mechanism is proposed to explain both this condensation and the known addition with nitroethane in excess base.

    5. C–H Activation

      Ruthenium-Catalyzed Alkenylation of Arenes with Alkynes or Alkenes by 1,2,3-Triazole-Directed C–H Activation

      Xing Guang Li, Kai Liu, Gang Zou and Pei Nian Liu

      Article first published online: 29 OCT 2014 | DOI: 10.1002/ejoc.201402938

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      The ruthenium-catalyzed alkenylation of arenes with unsaturated alkanes has been achieved by triazole-directed C–H activation. Dialkenylated arenes were efficiently produced by this method from internal alkynes as the sole products with high regio- and stereoselectivity.

    6. Allene Synthesis

      Highly Efficient Synthesis of Allenes from Trimethylaluminum Reagent and Propargyl Acetates Mediated by a Palladium Catalyst

      Qing-Han Li, Jung-Yuan Jeng and Han-Mou Gau

      Article first published online: 28 OCT 2014 | DOI: 10.1002/ejoc.201403008

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      Coupling reactions between trimethylaluminum and propargyl acetates catalyzed by palladium(II) acetate (1 mol-%) and tri(o-tolyl)phosphine (2 mol-%) were carried out in tetrahydrofuran at room temperature in 3 h to give the SN2′ substituted allenes in good to excellent yields of up to 94 %.

    7. Rare Sugar Synthesis

      Synthesis of All Eight Stereoisomeric 6-Deoxy-L-hexopyranosyl Donors – Trends in Using Stereoselective Reductions or Mitsunobu Epimerizations

      Tobias Gylling Frihed, Christian Marcus Pedersen and Mikael Bols

      Article first published online: 28 OCT 2014 | DOI: 10.1002/ejoc.201403074

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      The synthesis of all eight rare but biologically important 6-deoxy-L-hexoses as their thioglycoside glycosyl donors starting from L-rhamnose or L-fucose is reported. The synthesis was achieved using various epimerization methods. The stereoselective reduction of 4-oxo pyranosides could be predicted by the Cram chelation model, while Mitsunobu epimerization led to elimination in some substrates.

    8. Asymmetric Catalysis

      Chiral Squaramide-Catalyzed Sulfa-Michael/Aldol Cascade for the Asymmetric Synthesis of Spirocyclic Tetrahydrothiophene Chromanone Derivatives

      Bo-Liang Zhao, Lei Liu and Da-Ming Du

      Article first published online: 28 OCT 2014 | DOI: 10.1002/ejoc.201402889

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      A bifunctional squaramide-catalyzed sulfa-Michael/aldol cascade reaction between benzylidenechroman-4-ones and 1,4-dithiane-2,5-diol has been developed. This reaction enables facile asymmetric access to chiral spirocyclic tetrahydrothiophene chromanone derivatives with three contiguous stereocenters in high to excellent yields (up to 99 %) and with high enantioselectivities (up to 92 % ee).

    9. Arylenamide Synthesis

      Efficient Cross-Coupling of Dioxazaborocanes with α-Phosphate Enamides

      Nicolas Gigant, Aurélien Honraedt, Emmanuel Gras and Isabelle Gillaizeau

      Article first published online: 28 OCT 2014 | DOI: 10.1002/ejoc.201402927

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      A series of α-(hetero)arylenamides has been synthesized by Suzuki–Miyaura cross-couplings. Starting from simple α-phosphate enamides and air- and moisture-stable dioxazaborocanes, high yields were obtained through application of a slight excess of coupling partners.

    10. Carbocation Isomerization

      Mechanistic Elucidation of the 2-Nor­bornyl to 1,3-Dimethylcyclopentenyl Cation Isomerization

      Said Jalife, Gerardo Martínez-Guajardo, Claudia Zavala-Oseguera, María A. Fernández-Herrera, Paul von Ragué Schleyer and Gabriel Merino

      Article first published online: 27 OCT 2014 | DOI: 10.1002/ejoc.201403146

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      The mechanism for the 2-norbornyl (1) to 1,3-dimethylcyclopentenyl cation (16) isomerization has been elucidated by employing ab initio computations. Two viable complex pathways eventually converge to the same methylcyclohexenyl cation 11, which undergoes ring contraction, and methyl and hydride shifts to the target global minimum 16.

  33. Microreviews

    1. [2+2+2] Cycloaddition

      Recent Advances in Stereoselective [2+2+2] Cycloadditions

      Muriel Amatore and Corinne Aubert

      Article first published online: 21 OCT 2014 | DOI: 10.1002/ejoc.201403012

      Thumbnail image of graphical abstract

      [2+2+2] Cycloaddition reactions have achieved a leading position among the available tools for the construction of complex polycyclic molecules. The related asymmetric versions, now giving access to all chirality modes, are obviously more advantageous for the synthetic chemist. This review covers the recent advances in this field.

    2. Multicomponent Reactions

      The Ugi–Smiles and Passerini–Smiles Couplings: A Story About Phenols in Isocyanide-Based Multicomponent Reactions

      Laurent El Kaïm and Laurence Grimaud

      Article first published online: 19 OCT 2014 | DOI: 10.1002/ejoc.201402783

      Thumbnail image of graphical abstract

      The Ugi–Smiles and Passerini–Smiles couplings are isocyanide-based multicomponent reactions involving phenols and each featuring a Smiles rearrangement as a key step of the mechanism. Their scope, mechanistic studies, and the use of these couplings for a variety of routes to fused aromatic systems are reviewed here.

    3. Steroid Synthesis

      Asymmetric Assembly of Steroidal Tetracyclic Skeletons

      Preeti Gupta and Gautam Panda

      Article first published online: 9 OCT 2014 | DOI: 10.1002/ejoc.201402822

      Thumbnail image of graphical abstract

      The review highlights recent advances in the enantioselective synthesis of carbocyclic steroidal skeletons. Various synthetic approaches based on the use of chiral starting materials, reagent-controlled asymmetric induction and asymmetric synthesis with the aid of chiral auxiliaries are discussed.

    4. Natural Product Synthesis

      Neocryptolepine (Cryprotackieine), A Unique Bioactive Natural Product: Isolation, Synthesis, and Profile of Its Biological Activity

      Andrea B. J. Bracca, Daniel A. Heredia, Enrique L. Larghi and Teodoro S. Kaufman

      Article first published online: 6 OCT 2014 | DOI: 10.1002/ejoc.201402910

      Thumbnail image of graphical abstract

      Neocryptolepine is an indoloquinoline alkaloid, isolated from Cryptolepis sanguinolenta. The isolation of the natural product and the numerous and different approaches directed towards its total synthesis, as well as its biological activity profile and spectroscopic studies, are discussed.

    5. Manipulating Peptide Structures

      Heterogeneous Foldamers from Aliphatic–Aromatic Amino Acid Building Blocks: Current Trends and Future Prospects

      Roshna V. Nair, Kuruppanthara N. Vijayadas, Arup Roy and Gangadhar J. Sanjayan

      Article first published online: 18 SEP 2014 | DOI: 10.1002/ejoc.201402877

      Thumbnail image of graphical abstract

      This review is an effort to cover this rapidly developing field of foldamer science involving aliphatic-aromatic conjugate building blocks and to envisage its future perspectives.

    6. Vicinal Quaternary Stereocenters

      The Nazarov Cyclization: A Valuable Method to Synthesize Fully Substituted Carbon Stereocenters

      Donald R. Wenz and Javier Read de Alaniz

      Article first published online: 9 SEP 2014 | DOI: 10.1002/ejoc.201402825

      Thumbnail image of graphical abstract

      We describe three general approaches to the formation of fully substituted quaternary carbon stereocenters by means of the Nazarov cyclization.

  34. Full Papers

    1. Chelators for Bioconjugation

      Efficient Synthesis of 1,4,7-Triazacyclononane and 1,4,7-Triazacyclononane-Based Bifunctional Chelators for Bioconjugation

      Pauline Désogère, Yoann Rousselin, Sophie Poty, Claire Bernhard, Christine Goze, Frédéric Boschetti and Franck Denat

      Article first published online: 4 SEP 2014 | DOI: 10.1002/ejoc.201402708

      Thumbnail image of graphical abstract

      A new synthesis of 1,4,7-triazacyclononane and its N-functionalized derivatives is described. This powerful approach outperforms previous synthetic methods due to the use of an aminal intermediate. The method can be extended to the synthesis of valuable C-functionalized building blocks, giving access to a wide range of new bifunctional chelating agents, such as the p-NCS-Bz-MA-NOTA chelator.

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